CN102264656A - Electrostatically depositing conductive films during glass draw - Google Patents

Electrostatically depositing conductive films during glass draw Download PDF

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Publication number
CN102264656A
CN102264656A CN2009801531221A CN200980153122A CN102264656A CN 102264656 A CN102264656 A CN 102264656A CN 2009801531221 A CN2009801531221 A CN 2009801531221A CN 200980153122 A CN200980153122 A CN 200980153122A CN 102264656 A CN102264656 A CN 102264656A
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China
Prior art keywords
glass
conductive particle
glass baseplate
drawn
baseplate
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Pending
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CN2009801531221A
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Chinese (zh)
Inventor
C·R·费克特
A·V·菲利波夫
C·D·奥斯特蒙特
C·M·特鲁斯代尔
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Corning Inc
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Corning Inc
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23Oxides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/12General methods of coating; Devices therefor
    • C03C25/14Spraying
    • C03C25/143Spraying onto continuous fibres
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/42Coatings containing inorganic materials
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/42Coatings containing inorganic materials
    • C03C25/46Metals
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/211SnO2
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/215In2O3
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/216ZnO
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/24Doped oxides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/25Metals
    • C03C2217/268Other specific metals
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/11Deposition methods from solutions or suspensions
    • C03C2218/112Deposition methods from solutions or suspensions by spraying
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/11Deposition methods from solutions or suspensions
    • C03C2218/115Deposition methods from solutions or suspensions electro-enhanced deposition

Abstract

Methods for coating a glass substrate as it is being drawn, for example, during fusion draw or during fiber draw are described. The coatings are conductive coatings which can also be transparent. The conductive thin film coated glass substrates can be used in, for example, display devices, solar cell applications and in many other rapidly growing industries and applications.

Description

Electrostatic precipitation conducting film in the glass-pulling process
The application requires the right of priority of No. the 61/117th, 373, the U.S. Provisional Application of submitting on November 24th, 2008 and the U.S. Patent application of submitting on September 30th, 2009 the 12/570th, No. 762.
Background technology
Background technology
The glass that is coated with transparent conductive film can be used for a lot of application, for example is used for display applications, as the structure of display equipment (as liquid-crystal display (LCD)), and the Organic Light Emitting Diode (OLED) that is used for mobile phone.The glass that is coated with transparent conductive film can also be used for solar cell application, for example as the transparency electrode of the solar cell of some kinds, and be used for many other fast development industry and use.
Being used for the ordinary method of coated glass base material generally includes and material is carried out vacuum pump takes out, and before applying glass surface is cleaned, and before applying glass baseplate is heated, and deposits specific coating then.
Usually, in vacuum chamber, by sputter or chemical Vapor deposition process (CVD) (for example plasma fortified chemical Vapor deposition process (PECVD), depositing electrically conductive transparent film on glass baseplate.
At sputter transparent conductive film on glass; for example at the adulterated tin-oxide of sputtering sedimentation indium on glass; have following one or more shortcomings: the big area sputter has difficulties; consume for a long time; usually can on glass baseplate, form uneven film; particularly, for example be used for the display glass of televisor for the glass baseplate of size increase.
In some conventional coating methods, the cleaning glass that carried out before applying can cause complicacy and raise the cost.In addition, some conventional coating methods need mix to coating, and this operation of mixing is normally very difficult, needs other procedure of processing.
People need develop a kind of method, with conductive film coated glass base material, increase simultaneously coating density and/or reduce in the conventional coating method significantly morphology change as far as possible, can also reduce production costs simultaneously and shorten the production time.
Invention field
Embodiments of the present invention relate to the method that base material is applied of being used for, and more particularly, the present invention relates in the glass-pulling process by for example electrostatic precipitation, with the method for conductive film coated glass base material.
Summary of the invention
Method with conductive film coated glass base material of the present invention has solved the above-mentioned one or more defectives that exist in the conventional coating method, specifically, comprises in coating under the situation of metal and/or metal oxide.
In one embodiment, the present invention has disclosed a kind of method that is used in the process of glass-pulling coated glass base material.Described method comprises the drawn glass base material, applies the electric field that is close to the glass baseplate that is drawn, and makes the aerosol flow that comprises conductive particle by this electric field, drops on the glass baseplate that is drawn.
Supplementary features of the present invention and advantage have been proposed in the following detailed description, Partial Feature wherein and advantage are understood easily by described content to those skilled in the art, or are familiar with by implementing the present invention described in text description and its claims and the accompanying drawing.
The generality that should understand the front describes and the following detailed description all is to example of the present invention, is used to provide the character of the present invention of understanding institute's prescription and the overall commentary or the framework of characteristic.
The accompanying drawing that comprises provides further understanding of the present invention, and accompanying drawing is in this manual combined and constitute the part of specification sheets.Accompanying drawing illustrates one or more embodiment of the present invention, and is used for illustrating principle of the present invention and operation with specification sheets.
Brief Description Of Drawings
Can also understand the present invention in conjunction with the accompanying drawings by following detailed description or by following detailed description separately.
Figure 1A is according to an embodiment, in the drawn glass base material, glass baseplate is applied aerocolloidal side-view.
Figure 1B is according to the embodiment shown in Figure 1A, in the drawn glass base material, glass baseplate is applied aerocolloidal frontview.
Fig. 2 is according to an embodiment, in the drawn glass base material, glass baseplate is applied aerocolloidal synoptic diagram.
Fig. 3 is according to an embodiment, in the drawn glass base material, glass baseplate is applied aerocolloidal side-view.
Detailed Description Of The Invention
Below in detail with reference to various embodiments of the present invention, the example of these embodiments is shown in the drawings.
In one embodiment, the present invention has disclosed a kind of method that is used in the process of glass-pulling coated glass base material.Described method comprises the drawn glass base material, applies the electric field that is close to the glass baseplate that is drawn, and makes the aerosol flow that comprises conductive particle by this electric field, drops on the glass baseplate that is drawn.
According to an embodiment, described conductive particle comprises metal, metal oxide, metal halide, doping agent or their combination.Exemplary metal halide is SnCl 4, SnCl 2, SnBr 4, ZnCl 2, and their combination.Exemplary metal oxide is ZnO, SnO 2, In 2O 3, and their combination.Exemplary metal is Sn, Zn, In, and their combination.The diameter of described conductive particle can be 500 nanometers, for example is equal to or less than 200 nanometers, for example the 10-100 nanometer.
Method according to an embodiment also comprises the stream that uses following technology to produce conductive particle: spray pyrolysis, flame is synthetic, hot wall reactor, induction particle generator, spraying gun, perhaps their combination.
Hot wall reactor that can usage example, for example respond to particle generator, for example No. 11/881119 described device of No. the 2008/0035682nd, U.S. Patent Application Publication of submitting on July 25th, 2007 of owning together and U.S. Patent application produces aerosol flow.
The flame atomizing pyrolysis reactor of all right usage example, No. the 5th, 979,185, the United States Patent (USP) of for example owning together and the 6th, 260, No. 385 described devices prepare aerosol flow.According to an embodiment, described aerosol flow comprises the carrier gas that is used for conductive particle, for example nitrogen, oxygen etc., perhaps their combination and precursor, reactant, particle etc., and their combination.Described aerosol flow can comprise aerosol droplets or can comprise dried conductive particle.In one embodiment, the droplet diameter dimension of described aerosol droplets is equal to or less than 4000 nanometers, and for example, droplet size is the 10-1000 nanometer, for example is the 50-450 nanometer.
Be used for preparing in the chemical reaction process of conductive particle, making usually by the synthetic positively charged or negative charge of conductive particle that makes of gas phase.In one embodiment, described method also is included in and makes the aerosol flow that comprises conductive particle by before the electric field, makes conductive particle charged.According to an embodiment, make the charged step of conductive particle comprise and make the conductive particle stream that produces by comprising the charging zone of charger, to form charged conductive particle.Described charger can be selected from corona charging device, radioactive gas ionizer, photoelectricity charger, induction electricity charger and their combination.By using charger, can be so that conductive particle obtain electric charge from the air ion that charger produces, thus electric charge in the extra band.
Can be implemented in the extra particle charging in the charging zone by the combination of repeatedly charge mechanism or some charging mechanism effectively.The gaseous ion that for example, can be used for the particle charging by the preparation of radioactive gas ionizer.Can carry out radiation to aerosol by UV-light or the soft X-ray that produces with corresponding electromagnetic radiation source, thereby make aerosol particle charged (photoelectricity charging).
In No. the 7th, 393,385, No. the 7th, 361,207, the United States Patent (USP) of owning together and United States Patent (USP), the exemplary system that is used for electrostatic precipitation has been described.
In one embodiment, the conductive particle on the described glass baseplate is sintered, and forms conducting film.In one embodiment, described conducting film is transparent.Described conducting film can comprise metal, metal oxide, doping agent or their combination.In one embodiment, described conducting film comprises SnO 2, ZnO, In 2O 3, Zn, Sn, In, perhaps their combination.In one embodiment, described conducting film comprises the adulterated SnO of Cl 2, the adulterated SnO of F and Cl 2, the adulterated SnO of F 2, the adulterated In of Sn 2O 3, the adulterated ZnO of Al, the adulterated SnO of Cd 2, perhaps their combination.
In one embodiment, the thickness of described conductive film is equal to or less than 2000 nanometers, for example is the 10-1000 nanometer, for example is the 10-500 nanometer.
Described glass baseplate can be selected from glass fibre and glass ribbon.Exemplary drawing process comprises drop-down forming of glass, and for example fusion draws, pipe draws, slit draws and vertical drawing.An embodiment of the invention comprise that the glass ribbon to drawing from overflow groove in the fusion drawing process applies aerosol.
In the glass-pulling process, the initial glass surface of glass baseplate is normally unpolluted, can be used for deposition gas colloidal sol on glass baseplate very ideally, form conductive film then, why not comtaminated, part is because the temperature of glass baseplate, and because in the glass-pulling process, and glass baseplate only contacts with used equipment.Therefore, need before applying, not clean glass baseplate.
According to an embodiment, apply aerocolloidal step and comprise the glass baseplate that reaches or be lower than its second-order transition temperature is applied aerosol.
According to an embodiment, apply aerocolloidal step and be included in glass baseplate and aerosol put on glass baseplate when being elastic stage.
According to an embodiment, described method just is included in the drawn glass base material, and aerosol is put on glass baseplate, and the temperature of described glass baseplate is 200-800 ℃, for example is 350-600 ℃.In some applications, the upper limit of temperature range depends on the softening temperature of glass baseplate.Conducting film applies under the temperature of the softening temperature that is lower than glass baseplate usually.According to an embodiment, described conducting film forms under normal pressure.
Figure 1A and 1B have shown the feature 100 and 101 of the method for coated glass base material in fusion drawing process process.In this embodiment, the temperature of the glass baseplate 10 (glass ribbon) when leaving overflow groove 12 can be equal to or higher than 1100 ℃.Can be to regulating to the distance Y of carrying aerocolloidal equipment 16, with temperature corresponding to required glass ribbon from overflow groove outlet 14.Thereby the required temperature of glass ribbon can form metal oxide when for example metal refining is halid on glass ribbon and form the required temperature of glass baseplate 18 (in this embodiment for being coated with the glass ribbon of conductive film) that is coated with conductive film and determine.Similarly, can regulate, with corresponding to required aerosol speed the distance X from the aerosol flow to the glass ribbon.
Fig. 2 has shown in the fiber drawing process, the feature 200 of the method for coated glass base material.In this embodiment, the temperature of the glass baseplate 10 (glass fibre) when leaving process furnace 20 can be equal to or higher than 1100 ℃.Can to from furnace outlet 22 to carrying regulating of aerocolloidal equipment 16, with temperature corresponding to required glass fibre apart from B.According to another embodiment, can be to the distance of carrying aerocolloidal equipment from the cooling unit (not shown) apart from B.Thereby the required temperature of glass fibre can form metal oxide when for example metal refining is halid on glass fibre and form the required temperature of glass baseplate 18 (in this embodiment for being coated with the glass fibre of conductive film) that is coated with conductive film and determine.Similarly, can be to regulating to the distance A of glass fibre from carrying aerocolloidal equipment, with corresponding to required aerosol speed.
Can distance A and the B among the distance X among Figure 1A and Y or Fig. 2 be regulated, so that aerosol droplets or dried conductive particle are deposited on the glass baseplate.
In one embodiment, the step that applies electric field comprises one or more electrodes applied alternating-current (AC) or direct current (DC), producing electric field, thereby in the drawn glass base material, the charged conductive particle of deposition on glass baseplate.For example shown in the feature of the present invention 300 of Fig. 3, two opposite electrodes 26 and 28 that have an opposite charges can be arranged on the opposition side of the glass that is drawing.In drawn glass base material 10, apply the electric field that is close to the glass baseplate that is drawing with electrode 26 and 28, make the charged aerosol flow 24 that comprises conductive particle by electric field, drop on the glass baseplate, thus the coated glass base material.
The high capture efficiency of electrostatic precipitation technology can be so that even minimum particle (SnO for example 2Particle) also can be deposited on the base material.The temperature of the rising of base material can promote conductive particle attached on the base material, makes the conductive particle sintering form conducting film then.The cleanliness factor on initial glass surface can at utmost reduce the extra procedure of processing of before the film deposition glass being carried out.When film is sedimentary, do not need expensive vacuum system and complicated operations.Described deposition can be carried out under envrionment conditions, can be relatively easily the material of film be mixed/alloying.
Method of the present invention has versatility, can deposit the conductive film of independent kind, and many compositions film that deposition is complicated adds doping agent to film " original position ", and/or at utmost reduce air stream turbulence to guarantee the homogeneity of film.(Sn for example Zn) and does not use its high-temperature oxide (SnO for example to preferred deposition low-temperature evaporation metallics 2, ZnO), and by film partially sinter and/or the conversion of metal oxide is subsequently carried out in thermal treatment, this is because can (be 300 ℃ for Sn for example, for SnO under much lower temperature thus 2Be>1900 ℃) the preparation conducting film.The drawn glass temperature is enough high, can carry out the sintering of metallic particles.In general, the oxidation of metallics can be after pre-deposition, synthesis phase or deposition, be about to take place before the sintering.
To those skilled in the art, it is evident that, can under the situation that does not depart from the spirit or scope of the present invention, carry out various modifications and changes the present invention.Therefore, the invention is intended to is to cover modification of the present invention and change, as long as these modifications and change are within the scope of claims and equivalent thereof.

Claims (17)

1. the method for a coated glass base material in the glass-pulling process, described method comprises:
The drawn glass base material;
Apply the electric field that is close to glass baseplate to the glass baseplate that is drawn; And
Make the aerosol flow that comprises conductive particle by described electric field, drop on the glass baseplate that is being drawn.
2. the method for claim 1 is characterized in that, described method also comprises the stream that uses following technology to produce conductive particle: spray pyrolysis, flame is synthetic, hot wall reactor, induction particle generator, spraying gun, perhaps their combination.
3. the method for claim 1 is characterized in that, the conductive particle on the described glass baseplate is sintered to form conducting film.
4. method as claimed in claim 3 is characterized in that described conducting film is transparent.
5. method as claimed in claim 3 is characterized in that, described conducting film comprises metal, metal oxide, doping agent or their combination.
6. the method for claim 1 is characterized in that, described conductive particle comprises metal, metal oxide, metal halide, doping agent or their combination.
7. the method for claim 1 is characterized in that, described method also is included in and makes the aerosol flow that comprises conductive particle by before the electric field, makes that described conductive particle is charged.
8. method as claimed in claim 7 is characterized in that, makes the charged step of conductive particle comprise and makes the conductive particle stream that produces by comprising the charging zone of charger, to form charged conductive particle.
9. method as claimed in claim 8 is characterized in that described charger is selected from corona charging device, radioactive gas ionizer, photoelectricity charger, induction electricity charger and their combination.
10. method as claimed in claim 8, it is characterized in that the described step that applies electric field comprises one or more electrodes are applied alternating-current or direct current, to produce electric field, thereby in the drawn glass base material, the charged conductive particle of deposition on glass baseplate.
11. method as claimed in claim 10 is characterized in that, at two opposition sides of the glass that is just being drawn two opposite electrodes that have opposite charges is set.
12. the method for claim 1 is characterized in that aerosol flow comprises aerosol droplets.
13. the method for claim 1 is characterized in that, described glass baseplate is selected from glass fibre and glass ribbon.
14. the method for claim 1 is characterized in that, described method comprises the step that the glass baseplate that reaches or be lower than its second-order transition temperature is applied conductive particle.
15. the method for claim 1 is characterized in that, described method is included in the step that glass baseplate puts on described conductive particle when being elastic stage glass baseplate.
16. the method for claim 1 is characterized in that, described method is included in glass baseplate and is under 200-800 ℃ the situation of temperature, described conductive particle is put on the step of glass baseplate.
17. method as claimed in claim 16 is characterized in that, described method is included in glass baseplate and is under 350-600 ℃ the situation of temperature, described conductive particle is put on the step of glass baseplate.
CN2009801531221A 2008-11-24 2009-11-20 Electrostatically depositing conductive films during glass draw Pending CN102264656A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US11737308P 2008-11-24 2008-11-24
US61/117,373 2008-11-24
US12/570,762 2009-09-30
US12/570,762 US20100126227A1 (en) 2008-11-24 2009-09-30 Electrostatically depositing conductive films during glass draw
PCT/US2009/065254 WO2010059896A2 (en) 2008-11-24 2009-11-20 Electrostatically depositing conductive films during glass draw

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US (1) US20100126227A1 (en)
EP (1) EP2358648A2 (en)
JP (1) JP2012509829A (en)
CN (1) CN102264656A (en)
TW (1) TW201029942A (en)
WO (1) WO2010059896A2 (en)

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